Activated dihydroquinolines



United States Patent Ofiice 3,347,677 Patented Oct, 17, 1967 3,347,677 ACTIVATED DIHYDROQUINOLINES Ernest G. Jaworski, Olivette, and Gino J. Marco, Webster Groves, Mo., assignors to Monsanto Company, St. Louis, Mo., a corporation of Delaware N Drawing. Filed Apr. 1, 1966, Ser. No. 539,305 36 Claims. (Cl. 99-2) This application is a continuation-in-part of application Ser. No. 218,551 filed Aug. 22, 1962.

This invention relates to improved antioxidants and to methods of stabilizing substances subject to oxidative degradation. This invention further relates to animal feed compositions containing said improved antioxidants and to methods of feeding animals.

It has now been found in accordance with this invention that the antioxidant properties of well known antioxidants are significant-1y enhanced by admixture with certain nitrogen-containing compounds. The improved antioxidant compositions of this invention comprise a 2,2,4-trimethyl- 1,2-dihydroquinoline antioxidant of the formula Xn CH3 f on, H

wherein n is an integer from 0 to 2 inclusive and X is selected from the group consisting of chlorine, bromine and RO, wherein R is selected from the group consisting of hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the class consisting of alkyl having not more than 12 carbon atoms, alkenyl of not more than 12 carbon atoms, alkynyl of not more than 12 carbon atoms, cycloalkyl having at least 4 and not more than 7 carbon atoms, benzyl and phenyl, and wherein the substituents of not more than 4 carbon atoms on the hydrocarbyl are selected from the class consisting of alkyl, alkynyl and alkoxy, and a nitrogen-containing compound present in an amount sufficient to provide an enhanced antioxidant property, said compound having a formula selected from the group consisting of wherein Z is selected from the group consisting of oxygen, sulfur and imino, and R R R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 18 carbon atoms, alkenyl of not more than 18 carbon atoms, alkynyl of not more than 18 carbon atoms, phenyl and cycloalkyl of at least 4 and not more than 7 carbon atoms, and wherein the substituents on the hydrocarbyl are selected from the group consisting of nitro, hydroxyl, cyano, car-boxy], amino, phenyl, alkyl, alkylamino, dialkylamino, alkyloxy and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms,

wherein Z is selected from the group consisting of oxygen, imino and sulfur, and R R R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 18 carbon atoms, alkenyl of not more than 18 carbon atoms, alkynyl of not more than 18 carbon atoms, phenyl and cycloalkyl of at least 4 and not more than 7 carbon atoms, and wherein the substituents on the hydrocarbyl are selected from the group consisting of nitro, hydroxyl, cyano, carboxyl, amino, alkyl, phenyl, alkylamino, dialkylamino, alkyloxy and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms,

wherein Z contains a plurality of terminal nitrogen bonds and is selected from the group consisting of )s (SO2N )t wherein q and t are each integers from 1 to 6 inclusive, .9 is an integer from 1 to 3 inclusive and a1 is an integer from 2 to 12; R R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 18 carbon atoms, alkenyl of not more than 18 carbon atoms, alkynyl of not more than 18 carbon atoms, phenyl and cycloalkyl of at least 4 and not more than 7 carbon atoms, and 'Wherein the substituents on the hydrocarbyl are selected from the group consisting of nitro, hydroxyl, cyano, carboxyl, amino, phenyl, alkyl, alkylamino, dialkylamino, alkyloxy and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms, m is an integer from 2 to 3, n is an integer from 0 to 10 inclusive and p is an integer from 1 to 2,

wherein B contains a plurality of terminal nitrogen bond-s and is selected from the group consisting of wherein m is an integer from 2 to 3, e is an integer from 0 to 4 inclusive, b is an integer from 0 to 1, a is an integer from 2 to 12 inclusive; and R R and R are'each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 18 carbon atoms, alkenyl of not more than 18 carbon atoms, alkynyl of not more than 18 carbon atoms, phenyl and cycloalkyl of at least 4 and not more than 7 carbon atoms, and wherein the substituents on the hydrocarbyl are selected from the group consisting of nitro, hydroxyl, cyano,

carboxyl, amino, phenyl, alkyl, alkylamino, dialkylamino, alkyloxy and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms,

wherein R R R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 12 carbon atoms, alkenyl of not more than 12 carbon atoms, alkynyl of not more than 12 carbon atoms, phenyl, cycloalkyl of at least 4 and not more than 7 carbon atoms, and wherein the substituents on the hydrocarbyl are selected from the group consisting of alkyl, nitro, hydroxyl, cyano, carboxyl, amino, alkylamino, dialkylamino, phenyl, alkoxyl and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms, provide-d that not more than one of R and R and not more than one of R and R are selected from the group consisting of phenyl, substituted phenyl, benzyl, cyclohexyl and substituted cyclohexyl, and

wherein R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 12 carbon atoms, alkenyl of not more than 12 carbon atoms, alkynyl of not more than 12 carbon atoms, phenyl and cycloalkyl of at least 4 and not more than 7 carbon atoms, and wherein the substituents on the hydrocarbyl are selected from the group consisting of alkyl, nitro, hydroxyl, cyano, c-arboxyl, amino, alkylamine, phenyl, dialkylamino, alkoxy and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms, provided that not more than one of R and R is selected from the group consisting of phenyl, substituted phenyl, benzyl, cycloalkyl and substituted cycloalkyl; and Y is selected from the group consisting of R SH,

and the heterocyclic group wherein K is a heteronucleus selected from the group consisting of oxygen, sulfur, nitrogen and imino (NH) and D is a divalent hydrocarbon of at least three and not more than seven carbon atoms.

The following are representative of the nitrogen-containing compounds useful in the compositions and methods of this invention.

tetraethyldithiooxamide N,N-diphenyl dithiooxamide N,N'-diphenyl thiooxamide N,N-dioctyldecyl dithiooxamide N,N-dioleyl dithiooxamide N,N-dicyanoethyl thiooxamide N,N-bis (p-nitrophenyl) dithiooxamide dithiooxamide N,Ndimethyl thiooxamide N,N'-dimethyl dithiooxamide N,N-bis (carboxymethyl) dithiooxamide N,N-bis [2 (diethylamino) ethyl] dithiooxamide thiooxanilothiooxamide N,N-bis-(2-hydroxyethyl) dithiooxamide N,N'-dicyclohexy1 dithiooxamide 3 methoxydithiophthalimide 5 ethoxydithiophthalimide 4,5-dinitrodithiophthalimide 4-methoxythiophthalimide thiophthalimide dithiophthalimide bis-N thiocarb amoylmethylene) 1,4-benzenedisulfonamide 2,4,6-tris (thiocarbamoylmethylene) S-triazine 1,4-piperazine-bis (thioacetamide) N,N-bis (thiocarb amylmethylene) p-phenylenediamine dithiobiuret N,N-dithiocarbamoyl-1,4-piperizine 2,4,6-tris dimethylthiocarbamyl S-triazine N,N'-di(thiocarbamyl)ethy1enediamine-1,2

thiourea N,N-dimethyl thiourea N,N-di n-propyl) thiourea N,N'-diphenyl thiourea N,N'-di (tetradecyl thiourea thioacetamide A large number of the above described nitrogen-containing compounds which are useful in the compositions and methods of this invention are disclosed in the published literature and can be prepared by known methods. For example, the basic compound, rubeanic acid, can be prepared by reacting cyanogen with hydrogen sulfide. The rubeanic acid can be converted to other of the useful compounds by reaction with a primary or a secondary amine. Alternatively, the nitrogen containing compounds can be prepared from acid chlorides of carboxylic acids by reaction with amines, for example aniline, and thereafter converting the carbonyl groups to thiocarbonyl radicals.

The amount of nitrogen-containing compound necessary to provide enhanced antioxidant properties in the antioxidant compositions of this invention varies to some extent depending upon the specific dihydroquinoline antioxidant employed. The antioxidant compositions of this invention usually contain from about 0.05 part to about 20 parts by weight of nitrogen containing compound per one part by weight of dihydroquinoline antioxidant. Preferred compositions contain from about 0.33 part to about 10 parts by weight of nitrogen-containing compound per one part by weight of dihydroquinoline antioxidant. The improved antioxidant compositions of this invention can be incorporated into any substance which is subject to oxidative degradation in the presence of air, ozone, oxygen or various other oxidizing agents under the influence of heat, natural or artificial light, or various metals. The improved antioxidant compositions are added to the substance to be stabilized in any conventional manner. The components of the improved antioxidant compositions of this invention can also be added separately to the substances to be stabilized followed by conventional mixing to form the stabilized substance. Substances subject to oxidative degradation in which the improved antioxidant compositions of this invention are useful include for example unsaturated polymers such as natural rubber; synthetic rubber, e.g. butadiene and isoprene polymers and copolymers; petroleum based resins, e.g. coumarone indene; rosin and derivatives thereof, and high impact plastics, e.g. ABS, impact polystyrene, impact acrylics and impact PVC; saturated polymers such as hydrocarbon polymers, e.g. polyethylene, polypropylene, ethylene/ propylene copolymers and polyisobutylene; and food products, particularly those containing unsaturated oils, vitamins and vitamin containing components.

The antioxidant compositions of this invention are particularly useful for the stabilization of animal feeds containing components subject to oxidative degradation such as unsaturated oils, dehydrated alfalfa and other forage crops, vitamin concentrates, meal from oil processing industries, proteins and antibiotics.

It is Well known that the carotene in dehydrated alfalfa and other forage crops is subject to oxidative degradation and loss of vitamins, particularly vitamin A, under normal processing and storage conditions. Furthermore, animal feeds which include dehydrated forage crops and other vitamin-containing components can undergo further decomposition, such that animals to which they are fed are subject to malnutrition and more serious disabilities attributable to deficiencies in essential vitamins. It has also been found that many animals have the ability to store vitamins, and that the retention of these vitamins for future use is extended if antioxidants are included in the animal diets. The animal industry now regularly includes antioxidants as a conventional component in animal feeds.

The improved antioxidant compositions of this invention, when used in place of conventional amounts of dihydroquinoline antioxidants, give an equivalent level of antioxidant protection with less antioxidant or a more eifective level of antioxidant protection with the same amount of antioxidant. Thus, the compositions of this invention are usually employed in an amount equal to or less than the amount of antioxidant which is conventionally employed in the art.

The following examples illustrate the invention. Parts and percent are by weight unless otherwise indicated.

Example The antioxidant properties of nitrogen-containing compounds included within the scope of the generic formulae of this invention and closely related compounds not within the scope of this invention are determined by a standardized procedure using carotene emulsions and microanalysis techniques. The '6-ethoxy-2,2,4-trimethyl-1,2 dihydroquinoline is used as a standard for control and its antioxidant activity under identical conditions is assigned a rating of 100. The antioxidant activity of each nitrogen containing compound tested, both alone and in a one to three part admixture with the 6-ethoxy-2,2,4-trimethyl-1, Z-dihydroquinoline standard, is expressed as a percentage of the antioxidant rating of the standard. Results and further details are given in Table I.

TABLE I Antioxidant Activity Compound 1 part compound Alone plus 3 parts standard Standard; 6-ethoxy-2,2,4-trimethyl-l, 100

2-dihydroquinoline. Dithiooxamide 3. 184. O N,N-dimethylthiooxamide 1. 138. 6 N,N-dimethy1 dithiooxamide. 3. 0 163. 6 Thlooxanilinonitrile 0. 9 126. 3 O-Zinc salt S-allyl-N-dithiocarboxy- 3. 1 132. 9

N-phenyl-z-alanine. Thioacetanilide 2. 4 165. 7 N ,N-dicyclohexyl dithiooxamide 13. 6 127. 2 Rubeanic acid 0 187. 7 N ,N'-bis-2-ethyl meroaptoethyl ox- 3. 6 110. 7

amide. a-Anilino thioacetamide 4. 4 126. 0 Dithiobinret -3. 3 204. 9 Thiophthalimide 0.8 135. 8 Dithiophthalimide- 2. 9 146. 9 2-thiopicalinanilide 1. 2 145. 7 N,N:gis(2-hydroxyethy1) dithioox- 2. 6 121. 5

arm e. N ,N-bis(c arboxymethyl) dithioox- 2. 7 191. 9

amide. 'N,N-dibenzyl dithiooxamide 4. 7 161. 0 1,4-piperazine bis(thioacetamide) 0. 5 137. 1 N (thiocarbamoylmethylene)-p-t o l u 2. 4 151. 4

enesnlfonamide. 2-dimethylamino-4,6-bis(dimethyl- 1. 9 240 thiocarbamyD-S-triazine.

The following nitrogen-containing compounds are not within the scope of the useful compounds of the invention. The compounds have no beneficial activity and in some cases they adversely affect the antioxant properties of the dihydroquinoline standard.

TABLE II Antioxidant Activity Compound 1 Part compound Alone plus 3Parts standard Standard; 6-ethoxy-2,2,4-trimethyl-l,

2-dihydroquinoline. 28 Oxamide 0 103.0 29 N,N-bis-3-methoxypropyloxamide 4.6 55.3 30 1,1-dithiodiformamidine dihydrochloride. 0 97. 5 31 Dihexyl dithiooxalimldate -3.4 88.6 32 Thiododecanarnide 3.4 97.5 33 N,N-dimethyloxamide.. 0.9 103.9 34 N,N-dimethyl oxamide 3.5 103.9 35 Dimethyloxaldimidate 8.9 105.2

The antioxidant activity of various admixtures of rubeanic acid with the 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline standard is determined in order to demonstrate the relationship of the nitrogen-containing compounds to the antioxidant with respect to proportions of each. Results and further details are given below in Table III.

TABLE III Parts Antioxidant Wt. percent Activity Stan- Rnbeanic Standard RA dard=100 Acid Antioxidant The antioxidant compositions of this invention can be incorporation into any or all components of animal feed compositions in any convenient manner. Conventional animal feed compositions generally comprise at least about 2 percent plant ingredients such as hay, straw, silage, yellow corn, pasturage, ground corn cobs, cottonseed hulls, cotton mill wastes, beet pulp, corn meal, soybean oil meal, wheat bran, wheat middlings, dehydrated alfalfa, ground oats, millet, linseed oil meal, coconut oil meal, distillers dried grains, peanut oil meal, cottonseed meal and the like plant products. Most animal feed compositions also contain up to about 2 percent mineral ingredients such as bone meal, limestone, salt (N-aCl) and the various trace minerals including salt-s of zinc, copper, manganese, cobalt, iodine, iron and the like. Other materials which can be incorporated into animal feed compositions in varying amounts include animal ingredients such as fish meal, meat and bone scraps, dried milk, animal fats, dried whey solubles and the like; vitaminaceous ingredients such as vitamins A, B D and K, as well as the B vitamins such as riboflavin, niacin, pantothenic acid or salts thereof, choline, pyridoxine, thiamine, nicotinic acid or salts thereof, biotin, folic acid and the like; amino acids such as methionine, phenylalanine, arginine, glycine, histidine, isoleucine, leucine, lysine, threonine, tryptophan, valine and the like, and medicaments such as antibiotics, steroids, arsenicals, anthelmintics and the like.

Although the invention is described with respect to specific modifications, the details thereof are not to be construed as limitations except to the extent indicated in the following claims.

What is claimed is:

1. Antioxidant composition comprising an antioxidant of the formula X11 CH3 f CH3 H wherein n is an integer from to 2 inclusive and X is selected from the group consisting of chlorine, bromine and RO, wherein R is selected from the group consisting of hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the class consisting of alkyl of not more than 12 carbon atoms, alkenyl of not more than 12 carbon atoms, alkynyl [of not more than 12 carbon atoms, cycloalkyl having at least 4 and not more than 7 carbon atoms, benzyl and phenyl, and wherein the substituents of not more than 4 carbon atoms on the hydrocarbyl are selected from the class consisting of alkyl, alkynyl and alkoxy and a compound present in an amount sufiicient to provide an enhanced antioxidant property, said compound having a formula selected from the group consisting of (A) R Z s R wherein Z is selected from the group consisting of oxygen, sulfur and imino, and R R R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 18 carbon atoms, alkenyl of not more than 18 carbon atoms, alkynyl of not more than 18 carbon atoms, phenyl and cycloalkyl of at least 4 and not more than 7 carbon atoms, and wherein the substituents on the hydrocarbyl are selected from the group consisting of nitro, hydroxyl, cyano, car-boxyl, amino, phenyl, alkyl, alkylamino, dialkylamino, alkyloxy and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms,

( E r t a R C II Z wherein Z is selected from the group consisting of oxygen, imino and sulfur, and R R R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected .from the group consisting of alkyl of not more than 18 carbon atoms, alkenyl of not more than 18 carbon atoms,

alkynyl of not more than 18 carbon atoms, phenyl and cycloalkyl of at least 4 and not more than 7 carbon atoms, and wherein the substituents on the hydrocarbyl are selected from the group consisting of nitro, hydroxyl, cyano, carboxyl, amino, alkyl, phenyl, alkylamino, dialkylamino, alkyloxy and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms,

g [RI-LIZ (CHa) -N B: m wherein Z contains a plurality of terminal nitrogen bonds and is selected from the group consisting of wherein q and t are each integers from 1 to 6 inclusive, s is an integer from 1 to 3 inclusive and a is an integer from 2 to 12; R R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 18 carbon atoms, alkenyl of not more than 18 carbon atoms, alkynyl of not more than 18 carbon atoms, phenyl and cycloalkyl of at least 4 and not more than 7 carbon atoms, and wherein the substituents on the hydrocarbyl are selected from the group consisting of nitro, hydroxyl, cyano, carboxyl, amino, phenyl, alkyl, alkylamino, dialkylamino, alkyloxy and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms, m is an integer from 2 to 3, n is an integer from 0 to 10 inclusive .and p is an integer from 1 to 2,

wherein B contains a plurality of terminal nitrogen bonds and is selected from the group consisting of wherein m is an integer from 2 to 3, e is an integer from 0 to 4 inclusive, b is an integer from 0 to 1, a is an integer from 2 to 12 inclusive; and R R and R ,are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 18 carbon atoms, alkenyl of not more than 18 carbon atoms, alkynyl of not more than 18 carbon atoms, phenyl and cycloalkyl of at least 4 and not more than 7 carbon atoms, and wherein the substituents on the hydrocarbyl are selected from the group consisting of nitro, hydroxyl, cyano, carboxyl, amino, phenyl, alkyl, alkylamino, dialkylamino, alkyloxy and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms,

wherein R R R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 12 carbon atoms, alkenyl of not more than 12 carbon atoms, alkynyl of not more than 12 carbon atoms, phenyl, cycloalkyl of at least 4 and not more than 7 carbon .atoms, and wherein the substituents on the hydrocarbyl are selected from the group consisting of alkyl, nitro, hydroxyl, cyano, carboxyl, amino, alkyamino, dialkylamino, phenyl, alkoxyl and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms, provided that not more than one of R and R and not more than one of R and R are selected from the group consisting of phenyl, substituted phenyl, benzyl, cyclohexyl and substituted cyclohexyl, and

wherein R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 12 carbon atoms, alkenyl of not more than 12 carbon atoms, alkynyl of not more than 12 carbon atoms, phenyl and cycloalkyl of at least 4 and not more than 7 carbon atoms, and wherein the and the heterocyclic groups 'wherein K is a heteronucleus selected from the group consisting of oxygen, sulfur, nitrogen and imino (--NH-) and D is a divalent hydrocarbon of at least three and not more than seven carbon atoms.

2. Composition of claim 1 wherein the antioxidant is 6 ethoxy 2,2,4 trimethyl-l,2,-dihydroquinoline and the compound is represented by the formula s R3 H wherein Z is selected from the group consisting of oxygen, sulfur and irnino, and R R R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 18 carbon atoms, alkenyl of not more than 18 carbon atoms,

,alkynyl of not more than 18 carbon atoms, phenyl and ,cycloalkyl of at least 4 and not more than 7 carbon atoms,

and wherein the substituents on the hydrocarbyl are selected from the group consisting of nitro, hydroxyl, cyano,

carboxyl, amino, phenyl, alkyl, alkylamino, dialkylamino,

alkyloxy and alkylthio, the .alkyl moieties of said substituents having not more than 4 carbon atoms, and wherein the compound is present in an amount from about 0.05 part to about 20 parts by weight per one part by weight of the antioxidant. 3. Composition of claim 2 wherein the compound is rubeanic acid.

10 4. Composition of claim 1 wherein the antioxidant is 6 ethoxy 2,2,4-trimethyl-1,Z-dihydroquinoline and the compound is represented by the formula i R O wherein Z is. selected from the group consisting of oxygen, imino and sulfur, and R R, R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 18 carbon atoms, alkenyl of not more than 18 carbon atoms, alkynyl of not more than 18 carbon atoms, phenyl and cycloalkyl of at least 4 and not more than 7 carbon atoms, and wherein the substituents on the hydrocarbyl are selected from the group consisting of nitro, hydroxyl, cyano, carboxyl, amino, alkyl, phenyl, alkylamino, dialkylamino, alkyloxy and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms, and wherein the compound is present in an amount from about 0.05 part to about 20 parts by weight per one part by weight of the antioxidant.

5. Composition of claim 4 wherein the compound is dithiophthalimide.

6. Composition of claim 1 wherein the antioxidant is 6 ethoxy 2,2,4-tIimethyl-1,Z-dihydroquinoline and the compound is represented by the formula wherein Z contains a plurality of terminal nitrogen bonds and is selected from the group consisting of wherein q and t are each integers from 1 to 6 inclusive, s in an integer from 1 to 3 inclusive and a is an integer from 2 to 12; R R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hylrocarbyl is selected from the group consisting of alkyl of not more than 18 carbon atoms, alkenyl of not more than 18 carbon atoms, a1- kynyl of not more than 18 carbon atoms, phenyl and cycloalkyl of at least 4 and not more than 7 carbon atoms, and wherein the substituents on the hydrocarbyl are selected from the group consisting of nitro, hydroxyl, cyano, carboxyl, amino, phenyl, alkyl, alkylamino, dialkylamino, alkyloxy and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms, m is an integer from 2 to 3, n is an integer from 0 to 10 inclusive'and p is an integer from 1 to 2, and wherein the compound is present in an amount from about 0.05 part to about 20 parts by weight per one part by weight of the antioxidant.

7. Composition of claim 6 wherein the compound is 1,4-piperazine bis(thioacetamide).

8. Composition of claim 1 wherein the antioxidant is 6 ethoxy 2,2,4-trimethyl-1,Z-dihydroquinoline and the compound is represented by the formula wherein m is an integer from 2 to 3, e is an integer from to 4 inclusive, b is an integer from 0 to 1, a is an integer from 2 to 12 inclusive; and R R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 18 carbon atoms, alkenyl of not more than 18 carbon atoms, alkynyl of not more than 18 carbon atoms, phenyl and cycloalkyl of at least 4 and not more than 7 carbon atoms, and wherein the substituents on the hydrocarbyl are selected from the group consisting of nitro, hydroxyl, cyano, carboxyl, amino, phenyl, alkyl, alkylamino, dialkylamino, alkyloxy and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms, and wherein the compound is present in an amount from about 0.05 part to about 20 parts by weight per one part by weight of the antioxidant.

9. Composition of claim 8 wherein the compound is 2 dimethylamino 4,6 bis(dimethylthiocarbamyl)- S-triazine.

10. Composition of claim 1 wherein the antioxidant is 6-ethoxy-2,2,4-trimethyl 1,2 dihydroquinoline and the compound is represented by the formula wherein R R R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 12 carbon atoms, alkenyl of not more than 12 carbon atoms, alkynyl of not more than 12 carbon atoms, phenyl, cycloalkyl of at least 4 and not more than 7 carbon atoms, and wherein the substituents on the hydrocarbyl are selected from the group consisting of alkyl, nitro, hydroxyl, cyano, carboxyl, amino, alkylamino, dialkylamino, phenyl, alkoxyl and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms, provided that not more than one of R and R and not more than one of R and R are selected from the group consisting of phenyl, substituted phenyl, benzyl, cyclohexyl and substituted cyclohexyl, and wherein the compound is present in an amount from about 0.05 part to about 20 parts by weight per one part by weight of the antioxidant.

11. Composition of claim wherein the compound is diphenyl thiourea.

12. Composition of claim 1 wherein the antioxidant is 6-ethoxy-2,2,4 trimethyl 1,2 dihydroquinoline and the compound is represented by the formula 8 R Y 'lN wherein R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 12 carbon atoms, alkenyl of not more than 12 carbon atoms, alkynyl of not more than 12 carbon atoms, phenyl and cycloalkyl of at least 4 and not more than 7 carbon atoms, and

wherein the substituents on the hydrocarbyl are selected from the group consisting of alkyl, nitro, hydroxyl, cyano, carboxyl, amino, alkylamino, phenyl, dialkylamino, alkoxy and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms, provided that not more than one of R and R is selected from the group consisting of phenyl, substituted phenyl, benzyl, cycloalkyl and substituted cycloalkyl; and Y is selected from the group consisting of R -SH,

II R -sHHN 0 H2- and the heterocyclic group C D K wherein K is a heteronucleus selected from the group consisting of oxygen, sulfur, nitrogen and imino (NH-) and D is a divalent hydrocarbon of at least three and not more than seven carbon atoms, and wherein the compound is present in an amount from about 0.05 part to about 20 parts by weight per one part by weight of the antioxidant.

13. Composition of claim 12 wherein the compound is thioacetanilide.

14. Method of stabilizing a substance subject to oxidative degradation which comprises adding totthe substance an antioxidant of the formula Xn CH:

f OH; H

wherein n is an integer from 0 to 2 inclusive and X is selected from the group consisting of chlorine, bromine and RO, wherein R is selected from the group consisting of hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the class consisting of alkyl of not more than 12 carbon atoms, alkenyl of not more than 12 carbon atoms, alkynyl of not more than 12 carbon atoms, cycloalkyl having at least 4 and not more than 7 carbon atoms, benzyl and phenyl, and wherein the substituents of not more than 4 carbon atoms on the hydrocarbyl are selected from the class consisting of alkyl, alkynyl and alkoxy, and a compound present in an amount sufficient to provide an enhanced antioxidant property, said compound having a formula selected from the group consisting of wherein Z is selected from the group consisting of oxygen, sulfur and imino, and R R R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 18 carbon atoms, alkenyl of not more than (B) fi r C wherein Z is selected from the group consisting of oxygen, irnino and sulfur, and R R R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 18 carbon atoms, alkenyl of not more than 18 .carbon atoms, alkynyl of not more than 18 carbon atoms, phenyl and cycloalkyl of at least 4 and not more than 7 carbon atoms, and wherein the substituents on the hydrocarbyl are selected from the group consisting of nitro, hydroxyl, cyano, carboxyl, amino, alkyl, phenyl, alkylamino, dialkylamino, alkyloxy and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms,

v wherein Z contains a plurality of terminal nitrogen bonds and is selected from the group consisting of wherein q and t are each integers from 1 to 6 inclusive, 4

s; is; an integer from l to 3 inclusive and a is an integer from 2 to 12; R R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 18 carbon atoms, alkenyl of not more than 18 carbon atoms, alkynyl of not more than 18 carbon atoms, phenyl and cycloalkyl of at least 4 and not more than 7 carbon atoms, and wlierein the substituents on the hydrocarbyl are selected from the group consisting of nitro, hydroxyl, cyano, carboxyl, amino, phenyl, alkyl, alkylamino, dialkylamino, 'alkyloxy and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms, In is an integer from -2 to 3, n is an integer from 0 to 10 inclusive and p is an integer from 1 to 2,

wherein B contains a plurality of terminal nitrogen bonds and isls'electedffrom, the group consisting of wherein mis an integer from 2 to 3, e is an integer from 010 4 inclusive, b is an integer from 0 to 1, a is an integer from 2 to 12 inclusive; and R R and R are each se-" lected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocar byl is selected from the group consisting of alkyl of not more than 18 carbon atoms, alkenyl of not more than 18 carbon atoms, alkynyl of not more than 18 carbon atoms, phenyl and cycloalkyl of at least 4 and not more than 7 carbon atoms, and wherein the substituents on the hydro-' carbyl are selected from the group consisting of nitro,

hydroxyl, cyano, carboxyl, amino, phenyl, alkyl, alkylamino, dialkylamino, alkyloxy and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms, (E) T? N-C-N wherein R R, R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the group consistng of alkyl of not more than 12 carbon atoms, alkenyl of not more than 12 carbon atoms, alkynyl of not more than 12 carbon atoms, phenyl, cycloalkyl of at least 4 and not more than 7 carbon atoms, and wherein the substituents on the hydrocarbyl are selected from the group consisting of alkyl, nitro, hydroxyl, cyano, carboxyl, amino, alkylamino, dialkylamino, phenyl, alkoxyl and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms, provided that not more than one of R and R and not more than one of R cyclohexyl, and

wherein R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hy-. drocarbyl wherein the hydrocarbyl is selected from the,

group consisting of alkyl of not more than 12 carbon atoms, alkenyl of not more than 12 carbon atoms, alkynyl of not more than 12 carbon atoms, phenyl and cycloalkyl of at least 4 and not more than 7 carbon atoms, and wherein the substituents on the hydrocarbyl are selected from the group consisting of alkyl, nitro, hydroxyl, cyano, carboxyl, amino, alkylamino, phenyl, dialkylamino, alkoxy and alkylthio, the alkyl moieties of said substituents having not more than 4 car-bon atoms, provided that not more than one of R and R is selected from the group consisting of phenyl, substituted phenyl,- benzyl, cycloalkyl and substituted cycloalkyl; and Y is selected from the group consisting of R SH,

o l BJ-bHNOH and the heterocyclic group wherein K is a heteronucleus'selected from the group consisting of oxygen, sulfur, nitrogen and imino (--NH) and D is a divalent hydrocarbon of at least three and not more than seven carbon atoms. r A

15. Method of claim 14 wherein the antioxidant is 6- ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline and the compound is represented by the formula 1 wherein Z is selected from the group consisting of oxygen, sulfur and imino, and R R R and R? are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 18 carbon atoms, alkenyl of not more than 18 carbon atoms, alkynyl of not more than 18 carbon atoms, phenyl and cycloalkyl of at least 4 and not more than 7 carbon atoms, and wherein the substituents on the hydrocarbyl are selected from the group consisting of nitro, hydroxyl, cyano, carboxyl, amino, phenyl, alkyl, alkylamino, dialkylamino, alkyloxy and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms, and wherein the compound is present in an amount from about 0.05 part to about parts by weight per one part by weight of the antioxidant.

16. Method of claim 15 wherein the compound is rwbeanic acid.

17. Method of claim 14 wherein the antioxidant is 6-ethoxy-2,2,4-trimethyl 1,2 dihydroquinoline and the compound is represented by the formula l R C II Z wherein Z is selected from the group consisting of oxygen, imino and sulfur, and R R R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocanbyl wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 18 carbon atoms, alkenyl of not more than 18 carbon atoms, alkynyl of not more than 18 carbon atoms, phenyl and cycloalkyl of at least 4 and not more than 7 carbon atoms, and wherein the substituents on the hydrocarbyl are selected from the group consisting of nitro, hydroxyl, cyano, carboxyl, amino, alkyl, phenyl, alkylamino, dialkylamino, alkyloxy and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms, and wherein the compound is present in an amount from about 0.05 part to about 20 parts by weight per one part by weight of the antioxidant.

18. Method of claim 17 wherein the compound is dithiophthalimide.

19. Method of claim 14 wherein the antioxidant is 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline and the compound is represented by the formula wherein Z contains a plurality of terminal nitrogen bonds and is selected from the group consisting of wherein q and t are each integers from 1 to 6 inclusive, s is an integer from 1 to 3 inclusive and a is an integer from 2 to 12; R R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected 'firom the group consisting of alkyl of not more than 18 carbon atoms, alkenyl of not more than 18 carbon atoms, alkynyl of not more than 18 carbon atoms, phenyl and cycloalkyl of at least 4 and not more than 7 carbon atoms, and wherein the substituents on the hy- 16 drocarbyl are selected firom the group consisting of] nitro, hydroxyl, cyano, carboxyl, amino, phenyl, alkyl, alkylamino, dialkylamino, alkylox-y and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms, In is an integer from 2 to 3, n is an integer from 0 to 10 inclusive and p is an integer from 1 to 2, and wherein the compound is present in an amount from about 0.05 to about 20 parts by weight per one part by Weight of the antioxidant.

20. Method of claim 19 wherein the compound is 1,4- piperazine bis(thioacetamide).

21. Method of claim 14 wherein the antioxidant is 6 ethoxy-2,2,4 trimethyl 1,2 dihydroquinoline and the compound is represented by the formula wherein B contains a plurality of terminal nitrogen bonds and is selected from the group consisting of wherein m is an integer from 2 to 3, e is an integer from 0 to 4 inclusive, [2 is an integer from 0 to 1, a is an integer from 2 to 12 inclusive; and R R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 18 carbon atoms, alkenyl of not more than 18 carbon atoms, alkynyl of not more than 18 carbon atoms, phenyl and cycloalkyl of at least 4 and not more than 7 carbon atoms, and wherein the substituents on the hydrocarbyl are selected from the group consisting of nitro, hydroxyl, cyano, canboxyl, amino, phenyl, alkyl, alkylamino, dialkylamino, alkyloxy and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms, and wherein the com pound is present in an amount from about 0.05 part to about 20 parts by weight per one part by weight of the wherein R R R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted' hydrocarbyl wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 12 carbon atoms, alkenyl of not more than 12 carbon atoms, alkynyl of not more than 12 carbon atoms, phenyl, cycloalkyl of at least 4 and not more than 7 carbon atoms, and Wherein the substituents on the hydrocarbyl are selected from the group consisting of alkyl, nitro, hydroxyl, cyano, carboxyl, amino, alkylamino, dialkylamino, phenyl, alkoxyl and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms, provided that not more than one of R and R and ot more than one of R and R are selected from the group consisting of phenyl, substituted phenyl, benzyl, cyclohexyl and substi-I wherein R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 12 carbon atoms, alkenyl of not more than 12 carbon atoms, alkynyl of not more than 12 carbon atoms, phenyl and cycloalkyl of at least 4 and not more than 7 carbon atoms, and wherein the substituents on the hydrocarbyl are selected from the group consisting of alkyl, nitro, hydroxyl, cyano, carboxyl, amino, alkylarnino, phenyl, dialkylamino, alkoxy and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms, provided that not more than one R and R is selected from the group consisting of phenyl, substituted phenyl, benzyl, cycloalkyl and substituted cycloalkyl; and Y is selected from the group consisting of R SH,

and the heterocyclic group wherein K is a heteronucleus selected from the group consisting of oxygen, sulfur, nitrogen and imino (NH) and Dis a divalent hydrocarbon of at least three and not more than seven carbon atoms, and wherein the compound is present in an amount from about 0.05 part to about 20 parts by weight per one part by weight of the antioxidant. 26. Method of claim 25 wherein the compound is thioacetamide.

27. Animal feed composition containing as an essential ingredient therein an antioxidant composition comprising an antioxidant of the formula Xn CH I CH! wherein n is an integer from 0 to 2 inclusive and X is selected from the group consisting of chlorine, bromine and RO, wherein R is selected from the group consisting of hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the class consisting of alkyl of not more than 12 carbon atoms, alkenyl of not more than 12 carbon atoms, alkynyl of not more than 12 carbon atoms, cycloalkyl having at least 4 and not more than 7 carbon atoms, benzyl and phenyl, and wherein the substituents of not more than 4 carbon atoms on the hydrocarbyl are selected from the class consisting of alkyl, alkynyl and alkoxy, and a compound present in an amount sufiicient to provide an en- 18 hanced antioxidant property, said compound having a formula selected from the group consisting of wherein Z is selected from the group consisting of oxygen, sulfur and imino, and R R R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 18 carbon atoms, alkenyl of not more than 18 carbon atoms, alkynyl of not more than 18 carbon atoms, phenyl and cycloalkyl of at least 4 and not more than 7 carbon atoms, and wherein the substituents on the hydrocarbyl are selected from the group consisting of nitro, hydroxyl, cyano, carboxyl, amino, phenyl, alkyl, alkylamino, dialkylamino, alkyloxy and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms,

wherein Z is selected from the group consisting of oxygen, imino and sulfur, and R R R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 18 carbon atoms, alkenyl of not more than 18 carbon atoms, alkynyl of not more than 18 carbon atoms, phenyl and cycloalkyl of at least 4 and not more than 7 carbon atoms, and wherein the substituents on the hydrocarbyl are selected from the group consisting of nitro, hydroxyl, cyano, carboxyl, amino, alkyl, phenyl, alkylamino, dialkylamino, alkyloxy and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms,

wherein Z contains a plurality of terminal nitrogen bonds and is selected from the group consisting of wherein q and t are each integers from 1 to 6 inclusive, s is an integer from 1 to 3 inclusive and a is an integer from 2 to 12; R R and R are each selected from the group consisting of hydrogen, hy-.

carbon atoms, m is an integer from 2 to 3, n is an integer from to 10 inclusive and p is an integer from 1 to 2,

S R1 BFN wherein B contains a plurality of terminal nitrogen bonds and is selected from the group consisting of wherein m is an integer from 2 to 3, e is an integer from 0 to 4 inclusive, b is an integer from 0 to 1, a is an integer from 2 to 12 inclusive; and R R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 18 carbon atoms, alkenyl of not more than 18 carbon atoms, alkynyl of not more than 18 carbon atoms, phenyl and cycloalkyl of at least 4 and not more than 7 carbon atoms, and wherein the substituents on the hydrocarbyl are selected from the group consisting of nitro, hydroxyl, cyano, carboxyl, amino, phenyl, alkyl, alkylamino, dialkylamino, alkyloxy and alkythio, the alkyl moieties of said substituents having not more than 4 carbon atoms,

wherein R R R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 12 carbon atoms, alkenyl of not more than 12 carbon atoms, alkynyl of not more than 12 carbon atoms, phenyl, cycloalkyl of at least 4 and not more than 7 carbon atoms, and wherein the substituents on the hydrocarbyl are selected from the group consisting of alkyl, nitro, hydroxyl, cyano, carboxyl, amino, alkylamino, dialkylamino, phenyl, alkoxyl and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms, provided that not more than one of R and R and not more than one of R and R are selected from the group consisting of phenyl, substituted phenyl, benzyl, cyclohexyl and substituted cyclohexyl, and

s R" Yaw wherein R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 12 carbon atoms, alkenyl of not more than 12 carbon atoms, alkynyl of not more than 12 carbon atoms, phenyl and cycloalkyl of at least 4 and not more than 7 carbon atoms, and wherein the substituents on the hydrocarbyl are selected from the group consisting of alkyl, nitro, hydroxyl, cyano, carboxyl, amino, alkylamino, phenyl, dialkylamino, alkoxy and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms, provided that not 2% more than one of R and R is selected from the group consisting of phenyl, substituted phenyl, benzyl, cycloalkyl and substituted cyloalkyl; and Y is selected from the group consisting of R SH,

and the heterocyclic group K wherein K is a heteronuclens selected from the group consisting of oxygen, sulfur, nitrogen and imino (-NH--) and D is a divalent hydrocarbon of at least three and not more than seven carbon atoms. 28. Animal feed of claim 27 wherein the antioxidant is 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline and the compound is represented by the formula wherein Z is selected from the group consisting of oxygen, sulfur and imino, and R R R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 18 carbon atoms, alkenyl of not more than 18 carbon atoms, alkynyl of not more than 18 carbon atoms, phenyl and cycloalkyl of at least 4 and not more than 7 carbon atoms, and wherein the substituents on the hydrocarbyl are selected from the group consisting of nitro, hydroxyl, cyano, carboxyl, amino, phenyl, alkyl, alkylamino, dialkylamino, alkyloxy and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms, and wherein the compound is present in an amount from about 0.05 part to about 20 parts by Weight per one part by weight of the antioxidant.

29. Animal feed of claim 28 wherein the compound is rubeanic acid.

30. Animal feed of claim 27 wherein the antioxidant is 6 ethoxy 2,2,4-trimethyl-1,2-dihydroquinoline and the compound is represented by the formula wherein Z is selected from the group consisting of oxygen, imino and sulfur, and R R R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 18 carbon atoms, alkenyl of not more than 18 carbon atoms, alkynyl of not more than 18 carbon atoms, phenyl and cycloalkyl of at least 4 and not more than 7 carbon atoms, and wherein the substituents on the hydrocarbyl are selected from the group consisting of nitro, hydroxyl, cyano, carboxyl, amino, alkyl, phenyl, alkylamino, dialkylamino, alkyloxy and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms, and wherein the compound is present in an amount from about 0 .0 5 part to about 20 parts by Weight per one part by weight of the antioxidant.

31. Animal feed of claim 30 wherein the compound is dithiophthalimide.

a wherein Z contains a plurality of terminal nitrogen bonds and is selected from the group consisting of wherein q and t are each integers from 1 to 6 inclusive, s is an integer from 1 to 3 inclusive and a is an integer from 2 to 12; R R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 18 carbon atoms, alkenyl of not more than 18,carbon atoms, alkynyl of not more than 18 carbon atoms, phenyl and cycloalkyl of at least 4 and not more than 7 carbon atoms, and wherein the substituents on the hydrocarbyl are selected from the group consisting of nitro, hydroxyl, cyano, carboxyl, amino, phenyl, alkyl, alkylamino, dialkylamino, alkyloxy and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms, m' is an integer from 2 to 3, n is an integer from to 10 inclusive and p is an integer from 1 to 2, and wherein the compound is present in an amount from about 0.05 part to about parts by weight per one part by weight of the antioxidant.

33. Animal feed of claim 32 wherein the compound is 1,4-piperazine bis (thi'oacetamide) 34. Animal feed of claim 27 wherein the antioxidant is 6 ethoxy-2,2,4-trimethy1-1,2-dihydroquinoline and the compound is represented by the formula wherein B contains a plurality of terminal nitrogen bonds and is selected from the group consisting of phenyl and cycloalkyl of at least 4 and not more than 7 carbon atoms, and wherein the substitutents on the hydrocarbyl are selected from the group consisting of nitro, hydroxyl, cyano, carboxyl, amino, phenyl, alkyl, alkylamino, dialkylamino, alkyloxy and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms, and wherein the compound is present in an amount from about 0.05 part to about 20 parts by weight per one part by weight of the antioxidant.

35. Animal feed of claim 27 wherein the antioxidant is 6 ethoXy-2,2,4trimethyl-1,2-dihydroquinoline and the compound is represented by the formula wherein R R, R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 12 carbon atoms, alkenyl of not more than 12 carbon atoms, alkynyl of not more than 12 carbon atoms, phenyl, cycloalkyl of at least 4 and not more than 7 carbon atoms, and wherein the substituents on the hydrocarbyl are selected from the group consisting of alkyl, nitro, hydroxyl, cyano, carboxyl, amino, alkylamino, dialkylamino, phenyl, alkoxyl and alkylthio, the alkyl moieties of said substitutents having not more than 4 carbon atoms, rovided that not more than one of R and R and not more than one of R and R are selected from the group consisting of phenyl, substituted phenyl, benzyl, cyclohexyl and substituted cyclohexyl, and wherein the compound is present in an amount from about 0.05 part to about 20 parts by weight per one part by weight of the antioxidant.

36. Animal feed of claim 27 wherein the antioxidant is 6 ethoxy-2,2,4-trimethyl-1,2-dihydroquino1ine and the compound is represented by the formula 8 R" Y-( iN wherein R and R are each selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 12 carbon atoms, alkenyl of not more than 12 carbon atoms, alkynyl of not more than 12 carbon atoms, phenyl and cycloalkyl of at least 4 and not more than 7 carbon atoms, and wherein the substitutents on the hydrocarbyl are selected from the group consisting of alkyl, nitro, hydroxyl, cyano, carboxyl, amino, alkylamino, phenyl, dialkylamino, alkoxy and alkylthio, the alkyl moieties of said substituents having not more than 4 carbon atoms, provided that not more than one of R and R is selected from the group consisting of phenyl, substituted phenyl, benzyl, cycloalkyl and substituted cycloalkyl; and Y is selected fromthe group consisting of R SH,

about 20 parts by weight per one part by weight of the antioxidant.

(References on following page) 23 24 7 References Cited 3,141,775 7/1964 Surgent 999 3,149,117 7/1964 Brown 252402 UNITED STATES PATENTS 3,155,521 11/ 1964 Ward et a1. 99-2 10/1950 Levesque 260-551 3,156,690 11/1-964 Dexter Ct a1. 252402 10/1950 Levesque 260*247-1 3,278,308 10/1966 Marco 99-2 8/1951 ThOmPSOH- 3,279,921 10/1966 Jaworski 99'-2 6/1955 Bickofi 99-8 3,279,922 10/1966 Jaworski 99-2 5/1960 Bauley 99-32 X 8/1963 McKay et a1 A. LOUIS MONACELL, Primary Examzner. 2/ 1964 Brasen 252402 0 H. H. KLARE, Examiner. 

1. ANTIOXIDANT COMPOSITION COMPRISING AN ANTIOXIDANT OF THE FORMULA 